A flexible zinc tetrazolate framework exhibiting breathing behaviour on xenon adsorption and selective adsorption of xenon over other noble gases

Author(s): Shunshun Xiong ¹ ^, ² ^, ³ ^, ⁴ , Qiang Liu ¹ ^, ² ^, ³ ^, ⁴ , Qian Wang ¹ ^, ² ^, ³ ^, ⁴ , Wei Li ¹ ^, ² ^, ³ ^, ⁴ , Yuanming Tang ¹ ^, ² ^, ³ ^, ⁴ , Xiaolin Wang ¹ ^, ² ^, ³ ^, ⁴ , Sheng Hu ¹ ^, ² ^, ³ ^, ⁴ , Banglin Chen ⁵ ^, ⁶ ^, ⁷ ^, ⁸ ^, ⁹

Publication date (Electronic): 2015

Journal: Journal of Materials Chemistry A

Publisher: Royal Society of Chemistry (RSC)

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Abstract

We present a flexible zinc tetrazolate framework with breathing behaviour on Xe adsorption and significantly high Xe/Kr selectivity under flow condition.

Abstract

Given the fact that traditional cryogenic rectification is highly energy and capital intensive for the purification of xenon, effective selective adsorption of xenon over other noble gases at room temperature using porous materials is a critical and urgent issue. Here, we present a flexible zinc tetrazolate framework ([Zn(mtz) ₂]), which exhibits a high capture capacity for xenon and selective adsorption of xenon over other noble gases at room temperature. Due to its high adsorption enthalpy for xenon, a suitable pore size that matches well with the xenon atom, as well as the high polarizability of Xe, [Zn(mtz) ₂] shows breathing behaviour on xenon adsorption, which is confirmed by the experimental adsorption isotherms of xenon and thermodynamic analysis of breathing transition. The isosteric heats of adsorption and S(DIH) calculations indicate that [Zn(mtz) ₂] has significantly higher adsorption affinity and capacity for Xe compared with Kr, Ar and N ₂. The high capture capacity of Xe (2.7 mmol g ⁻¹) in an idealized PSA process and high Xe/Kr selectivity (15.5) from breakthrough experiment promise the potential application of [Zn(mtz) ₂] in Xe capture and separation from Xe–Kr gas mixtures.

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Selective gas adsorption and separation in metal-organic frameworks.

Jian-Rong Li, Ryan J Kuppler, Hong-Cai Zhou (2009)

Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal-organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).